Method of making 4,4&#39;-di(halomethyl) diphenyl oxides and product



. 3,004,072 v Patented Oct. 10, 1 1

bromic acid is Substituted for the hydrochloric acid when 2 .the bromomethyl analog is desired. About 10-40 per- METHOD OF MAHNG 4,4 'nlmALoMETHYL) cent acetic acid, advantageously as 90-100 percent HOAc, DIPHENYL OXIDES AND PRODUCT as a solvent and about 15-30 weight percent concentrated James D. Doedens, Midland, and Earl H. Rosenbrock, Sulfuric acid as catalyst (or an equivalent amount of,

g gi zg g gggsg om concentrated phosphoric acid), both acetic acid and sul- No Drawing. Filed Man 26, 1959, Sen -301,93 L furic acid being calculated as weight percent of total 2 Claims. (Cl. 2605-612) 7 v reaction mediurn, are utilized. Preferably equal concentrations of acetic and sulfuric acids are used to give This invention concerns a method for preparing 4,4'- maximum yields. A reaction temperature of about 70 di(halomethyl)diphenyl oxides, halo being inclusive of to 100 C. for about A to about 3 hours, preferably chloro and bromo, and the new compound 4,4'-di(bromo 90-100 C. for about A to 1 hours, is used.

methyl)diphenyl oxide. Hereinafter, reference to these The reaction product is separated from the reaction compounds will be as 4,4'-DHMDPO, 4,4-DCMDPO medium'b'y'cooling it to 20-30 C to crystallize prodand 4,4'-DBMDPO, respectively. uct 4,4 -DHMDPO and separating and washing the prod- It has been reported that 4,4-DCMDPO has been preuct crystals with water until the wash water is neutral. pared by reacting proportions of 1 mole diphenyl oxide Additional crystals-are recovered from the organic phase (hereinfter referred to as DPO), 2 moles formalin by washing it with water, drying it over anhydrous cal- (CH O basis), aqueous zinc chloride (50 weight percent, cium sulfate and crystallizing by cooling to C. DPO basis) anhydrous HCl and HOAc'as follows. The 20 In practice, acharge of DPO, par'aformaldehyde, conanhydrous HCl is added at a rapid rate to the reaction centrated hydrochloric or hydrobrornic acid, acetic acid mixture at 98l00 C. After about 3 hours, the re: and sulfuric acid (or phosphoric acid) is added, the lataction mixture is cooled, extracted several times ;with 'ter gradually, to a reaction vessel provided with an agidiethyl ether, the extracts are washed with water and tator, thermometer and reflux condenser. The mixture aqueous sodium carbonate, dried over anhydrous sodium is heated at 90-100 C. until reaction has proceeded to sulfate and fractionally distilled under reduced pressure, maximum yield, advantageously for to l /ahours, whereby 4,4-DCMDPO isrecovered. This method gives and preferably for 1 hour at 90 C. The reaction mixa mixture of monoand DCMDPO and low molecular t e s then c oled to 2030 C. and dropped into a weight polymeric products. Separation of'products is separatory funnel 'where crystals of product 4,4- difficult. Several ether extractions and a distillation are go-DHMDPO are, separated from the aqueous phase and utilized. Upon distillation, decomposition of the wanted water washed until washings are neutral. The organic DCMDPO occurs booallso ob ig Point f DCMDPO., phase is then separated from the aqueous phase, water. is (31058 to its decomposition temperature. evolved washed several times over anhydrous calcium $111.. on decomposition t oatalyzes Polymerization to W fate and cooled to 20 0. to crystallize out additional and Polymenc 7 Also the Zmc Phlonde product. The total yield so obtained ranges between cimnot be completaily TemOVedJfi9m i about and about percent, DPO basis, of a come {:3 rg gsg Its 9 to polymeric l mercially satisfactory .4,4-DHMDPO product. ,If a ry pure product is desired, recrystallization is carried out;

The difliculties of the prior art have been overcome to a marked degrefi by the process of this invention 40 by dissolving the commerclal product 1n toluene and pre wherein yields as as about 75 percent 4,4-DHMDPO; cipitaflilg with commrcial i i of Octane by DPO basis, can be obtained. The process comprises d1sS1v1 ng the i? wlth a commerclal reacting a mixture of proportions of. 1 mole DPO to time mlxture and f f to crystamzauon' about 2-4 moles formaldehyde, advantageously as para-. The Procedure mdlcated above was mulled Wlth formaldehyde to about 3-4 moles hydrogen chloride, as 45 Solis. d comparisons with other Procedures as given concentrated hydrochloric acid. Concentrated hydrointhe following tables.

EXAMPLE 1 7 Table l.-Chl0r0methylati0n'of diphenyl oxidewith sulfuric acid catalyst 1 H0110] Cone. Wt. Grams Wt. Rxn. Rxn. Per- Run DPO DPO, HOHO, H01, Grams Per- Cone. percent time, temp., cent No. molar g. g. g. EOAc cent H2804 H1804 hrs. 0. Yield HOAc . EXAMPLE 2 Acetic acid content in the reaction medium was varied with the following results.

Table [1 EUR Cone. Wt. Wt. Rxn. Rxn. Per- Run DPO DPO, ECHO, H01, HOAc, percent H2804, per- Time, temp, cent N 0. molar g. g. g. g. HOAc, g. cent hrs. 0. Yield 1 3 340 180 667 500 23. 2 497 23. 2 l. 98 63 2 3 340 180 667 250 13. l 497 26. 0 l. 0 98 46 3 3 340 180 667 None 0 497 30.0 1.0 94 11 4 3 340 180 667 l, 000 37. 5 497 18. 6 1. 0 94 44. 5

EXAMPLE 3 I Reaction time was varied with the following results.

Table III Run HOHO/ DPO, HCHO, Cone. HOAc, Cone. Rxn. Rxn. 4,4-DOMDPO, Per- N o. DPO, g. g. H01, g. H2804 time, temp., g. cent molar hrs. 0. yield 1- 3 340 180 667 500 497 1 94 333 63 2-.. 3 340 180 667 500 497 2 94 203 38 3-.." 340 180 667 500 497 3 94 144. 5 26 EXAMPLE 4 Concentrated phosphoric acid was substituted for the sulfuric acid catalyst with the following result.

Table IV DPO, HOHO, Cone. Cone. Rxn. Rxn. 4,4-DGMDPO, Per- HCHO/DPO molar g. g. HCl, H3PO HOAc, g. time, temp., g. cent a g. g. 7 hrs, 0. yield 3 340 180 667 497 500 (22.8 percent 4. 5 98 286 54 of mi. mix.).

The 4,4-DCMDPO product recrystallized from a commercial octane hydrocarbon solvent mixture boiling 'between 100 and 140 0, had a molecular formula of C H OCl a molecular weight of 267, a melting range of 62.4-63" C. (62.4 C. theoretic), and a chlorine content of 26.2 percent (26.5 percent of dichloromethyldiphenyl oxide). 1

EXAMPLE 5 A quantity of 510 g. diphenyl oxide (3.0 mol.), 270 g. paraformaldehyde (9.0 mol. CH O), 1630 g. aqueous 48 percent hydrobromic acid (9.6 mol.), 740 g. conc. sulfuric acid, and 750 g. acetic acid was added to a 3- -liter three-necked flash equipped with a mechanical stirrer, thermometer, and reflux condenser. The'r'eaction mixture was heated at reflux for 1 hour at 90-95 C. with agitation. It was then cooled to -30 C. and the aqueous phase was separated. The organic layer was slurried with warm water and during this time the product crystallized. The material was filtered on a Buchner funnel, Washed several times with water, and air dried at room temperature for several days.

dissolved in 6250 ml. of a commercial octane mixture, (2., by heating to7580 C; The solw tion was allowed to cool and the resulting crystals were filtered off to give 782.3 g. of 4,4'-DBMDPO crystals, 73 percent yiel The crystals were white and acicular, melted at 9496 C., had a molecular weight of 356.08 and'a molecular formula of C H OBr A substantially'pure 4,4'-DBMDPO was recrystallized by dissolving one part of 4,4'-DBMDPO, as above,"in 7;7 parts'of a commercial octane, B.R. 100-140 C. by heating to 6 O65 C., cooling to 20 C. and filtering off the resulting crystals. The resulting product had a melting point of 96 C., and consisted of 4,4- DBMDPO having a trace of monobromomethyl DPO, as determined by infrared analysis.

EXAMPLE 6 equipped with a mechanical stirrer, thermometer, gas sparging'tube, andrefiux condenser. The reaction mixture was heated to 70 C. over a one hour period, then held at this temperature for 2 hours. The reaction was sparged with anhydrous HCl during the entire course of the reaction. The reacted mixture was then cooled to 50 -55 C. and the aqueous layer was separated. The organic layer was washed twice with60" C. water, then with a 5 percent'solution of sodium bicarbonate at 60 C., and finally with one more water wash. The organic layer was then cooled to 20-25 C. to allow crystallize tion. A quantity of 228 g. (41 percent yield) of 4,4- DCMDPO crystals recovered, having a melting point of 6265 C. In addition, 295 g. mother liquor was also recovered.

At a concentration of 10 p.p.m., 4,4'-DBMDPO was percent elfective in was plated in rosebeng'al-streptomycin agar and incubated for 64 hours in the usual way. In comparison thereto,-the' known chloro'analog, 4,4'-DCMDPO, showed no inhib'itive effect under Y What is claimed is:

1. A method for making a 4,4'-dihalomethyl diphenyl oxide wherein halo is a member of the group consisting similar test conditions.

of chloro and bromo, which method comprises heating a mixture of proportions of 1 mole diphenyl oxide, about 2 to about 4 moles of formaldehyde, about 2 to about 4 moles of a concentrated hydrogen halide of the group consisting of hydrochloric and hydrobromic acid, about to about 40 weight percent of concentrated acetic acid, total reactants basis, and about to about weight percent of a concentrated mineral acid of the group consisting of sulfuric and phosphoric acid, total reactants basis, at a temperature ranging between about and about C. for a time ranging between about A. and about 3 hours, dependent upon temperature, and separating dihalomethyl diphenyl oxide product.

2. 4,4'-di(bromomethyl)diphenyl oxide, a white, crys- (BICH2C H4) 0 wherein the bromomethyl groups are in the 4,4'-positions.

References Cited in the file of this patent FOREIGN PATENTS Germany Feb. 4, 1933 OTHER REFERENCES Adams ct a1.: Organic Reactions, pages 69, 70, 72.

volume I (1954), 

1. A METHOD FOR MAKING A 4,4''-DIHALOMETHYL DIPHENYL OXIDE WHEREIN HALO IS A MEMBER OF THE GROUP CONSISTING OF CHLORO AND BROMO, WHICH METHOD COMPRISES HEATING A MIXTURE OF PROPORTIONS OF 1 MOLE DIPHENYL OXIDE, ABOUT 2 TO ABOUT 4 MOLES OF FORMALDEHYDE, ABOUT 2 TO ABOUT 4 MOLES OF A CONCENTRATED HYDROGEN HALIDE OF THE GROUP CONSISTING OF HYDROCHLORIC AND HYDROBROMIC ACID, ABOUT 10 TO ABOUT 40 WEIGHT PERCENT OF CONCENTRATED ACETIC ACID, TOTAL REACTANTS BASIS, AND ABOUT 15 TO ABOUT 30 WEIGHT PERCENT OF A CONCENTRATED MINERAL ACID OF THE GROUP CONSISTING OF SULFURIC AND PHOSPHORIC ACID, TOTAL REACTANTS BASIS, AT A TEMPERATURE RANGING BETWEEN ABOUT 70* AND ABOUT 100*C. FOR A TIME RANGING BETWEEN ABOUT 3/4 AND ABOUT 3 HOURS, DEPENDENT UPON TEMPERATURE, AND SEPARATING DIHALOMETHYL DIPHENYL OXIDE PRODUCT. 